Phosphorus acid ester-containing pesticidal composition and methods of combating pests

ABSTRACT

Compositions and methods of using phosphoryl-, phosphonyl-, thionophosphoryl- and thionophosphonyl- - Alpha -oximinoarylacetic acid nitriles which possess pesticidal, especially insecticidal and/or acaricidal, properties, and which may be produced by reacting the corresponding phosphorus acid ester halide with the corresponding Alpha -oximino-arylacetic acid nitrile.

United States Patent Lorenz et al.

[ 1 Sept. 5, 1972 [54] PHOSPHORUS ACID ESTER- CONTAINING PESTICIDAL COMPOSITION AND METHODS OF COMBATING PESTS [72] Inventors: Walter Lorenz, Wuppertal-Vohwinkel; Christa Fest, Wuppertal-Elberfeld; Ingeborg Hammann, Cologne; Manfred Federmann; Winfried Flucke, both of Wuppertal-Elberfeld; Wilhelm Stendel, Wuppertal-Vohwinkel, all of Germany [73] Assignee: Farbenlabrlken Bayer Alrfiengesellschaft, Leverkusen, Germany [22] Filed: Oct. 24, 1968 [21] Appl. No.: 792,876

Rehted US. Application Data [62] Division of Ser. No. 553,031, May 26, 1966,

Pat. No. 3,591,662.

[52] US. Cl. ..424/2I0 [5 1] Int. Cl. ..A0ln 9/36 [58] neldotsw-ch ..424/2l0 [56] References Cited UNITED STATES PATENTS 3,469,004 9/ 1969 Kaufman et al. ..........424l2l0 Pn'maiy Examiner-Sam Rosen Attorney-Burgess, Dinklage and Sprung ABSTRACT 18 Claims, No Drawings PHOSPl-IORUS ACID ESTER-CONTAINING PESTICIDAL COMPOSITION AND METHODS OF COMBATING PESTS This application is a division of copending US. application, Ser. No. 553,031, filed May 26, 1966 now US. Pat. No. 3,591,622.

The present invention relates to particular new phosphoryl-, phosphonyl-, thionophosphoryland thionophosphonyl- -a-oximino-arylacetic acid nitriles having pesticidal, especially insecticidal and/or acaricidal, properties, to their compositions with dispersible carrier vehicles, and to methods for the preparation and use thereof.

It is already known that 0,0-dialkyl-phosphoryl oximines can be prepared by reacting geminal halo-nitroor -nitroso-alkanes with 0,0,0-trialkyl-phosphorus acid esters in accordance with the following equation in which R, R and R" represent alkyl radicals and Hal is preferably chlorine (cf. J.F. Allen, .I.A.C.S., 79,

From German Pat. Specification No. 1,052,981, there is also known, inter alia, the reaction of 0,0-dialkyl-phosphoric or -thionophosphoric acid ester halides with oximes, preferably ketoximes, such as acetoxime. 4-chloro-acetophenon or cyclohexanone-oxime, in the form of their alkali metal salts or in the presence of agents which bind hydrogen halide, leading to 0,0-dialkyl-(thiono)phosphoryl oximes, according to the following equation in which R and R" are alkyl radicals:

Finally, it is also possible, according to German Pat. Specification No. 962,608, to react cyclic dicarboxylic acid hydroximides in the form of their alkali metal salts or in the presence of acid-binding agents, such as the oximes of ketones, with 0,0-dialkyl-phosphoric or thiono-phosphoric acid ester chlorides to form the corresponding N-(0,0,-dialkyl-phosphoryl or thionophosphoryl )-diacyl imides, for example:

None of the methods of production known from the literature, however, leads to the phosphorylor thionophosphoryl-a-oximino-arylacetic acid nitriles of the present invention.

It is an object of the present invention to provide particular new phosphorus-containing esters, and especially phosphoryl-, phosphonyl-, thionophosphoryland thionophosphonyl-a-oximinoarylacetic acid nitriles, having valuable pesticidal, and especially arthropodicidal, properties; to provide pesticidal compositions in the form of mixtures of such compounds with liquid and solid dispersible carrier vehicles; to provide processes for preparing such compounds; and to provide methods of using such compounds in a new way especially for combating pests, such as insects and/or acarids.

Other and further objects of the present invention will become apparent from a study of the within specification and accompanying examples.

It has now been found, in accordance with the present invention, advantageously that the particular new phosphorus-containing a-oximino-aryl acetic acid nitriies having the formula:

in which R, is selected from the group consisting of alkyl having one to six carbon atoms, and haloalkyl having one to six carbon atoms, R, is selected from the group consisting of alkyl having one to four carbon atoms, alkoxy having one to four carbon atoms, haloalkoxy having one to four carbon atoms, lower alkyl amino, di(lower) alkyl amino, phenyl, phenoxy, cyclohexyl, and cyclohexyloxy, R, is selected from the group consisting of phenyl, naphthyl, pyridyl, and substituted phenyl which is substituted with substituents selected from the group consisting of mono-, di-, and tri-halo, lower alkyl, lower alkoxy, lower alkyl mercapto, nitro, and mixtures thereof, and X is selected from the group consisting of oxygen and sulfur, possess valu able strong biocidal, for example pesticidal, and especially insecticidal and acaricidal, properties.

It has been further found in accordance with the present invention that a process for producing the compounds of formula (I) above, readily and in good yields, may now be provided, which comprises reacting ester halide having the formula:

V R; (H8) in which R, is the same as defined above, in the form of its corresponding salt, especially alkali metal salt, such as sodium or potassium salt, and alkaline earth metal salt, such as calcium, barium or strontium salt, as well as heavy metal salt, such as silver salt, or in the presence of acid-binding agents.

The course of the reaction is illustrated in greater detail by means of the following equation:

in this equation, R,, 11,, 11,, Hal and X are the same as defined above.

Some of the a-oximino compounds used as starting materials for carrying out the process according to the present invention, for example, a-oximino-phenylacetic acid nitrile and its derivatives substituted in the phenyl nucleus, as well as the salts of these compounds have been described in the literature. Where such starting materials are new, they can be prepared by known methods. If the a-oxirnino-arylacetic acid nitriles occur in the form of two detectable and stable isomers (synand anti-form), this is of no importance for carrying out the reaction.

The reaction is preferably carried out in the presence of solvents or diluents. Low-boiling aliphatic-itetones and -nitriles, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, acetonitrile, and propionitrile, and also optionally chlorinated aromatic or aliphatic hydrocarbons, such as benzene, toluene, xylenes, chlorobenzenes, methylene chloride, chloroform, carbon tetrachloride and mono-, diand trichloroethylene, are preferred solvents. Finally, the reaction can also be carried out with the use of water as solvent, provided that the reactivity of the ester halides used permits this procedure.

As has already been mentioned above, the process according to the present invention is carried out with the use of salts of a-oximino-arylacetic acid nitriles. Alkali metal and alkaline earth metal salts, but also heavy metal salts (e.g., of silver), are mainly to be considered for this purpose. Instead of starting from these salts, it is also possible to use, with equally good results, the corresponding free a-oximino compounds as starting materials and to react these in the presence of acidbinding agents. Preferred examples of acid-binding agents are alkali metal carbonates and alcoholates, such as potassium and sodium carbonate, methylate and ethylate, as well as tertiary bases, for example, triethylamine, diethyl-aniline or pyridine.

The process can be carried out within a fairly wide range of temperature. in general, the operation is performed at room temperature or slightly to moderately elevated temperature, preferably at to 30 C. Since, however, the reaction usually proceeds with a more or less pronounced positive heat effect, it is frequency necessary to cool the mixture externally, especially at the start of the reaction. Finally, it has proved expedient, in order to complete the reaction, to stir the mixture for some time (1 to 3 hours or overnight) after the starting components have been combined, with slight heating, if necessary.

The compounds according to the present invention are usually colorless to slightly yellow colored, waterinsoluble oils which can only be distilled in small amounts, even under strongly reduced pressure, because they are sensitive to the prolonged action of an elevated temperature; some of the new compounds occur in the form of colorless crystalline compounds which can easily be further purified by recrystallization from conventional solvents or solvent mixtures.

The new phosphorus-containing esters according to the present invention have an extremely low toxicity towards warm-blooded animals and an outstanding biocidal, especially insecticidal and acaricidal, activity which commences rapidly. The compounds can therefore, be successfully used in plant protection for combating noxious sucking and biting insects, Diprera and mites (Acan').

The sucking insects essentially include the aphids (A- phidae), such as Myzus persicae, Dorali: fabae, Rhopalosiphum pedi., Macrosiphum pisi and Macrosiphum solamj'olii, furthermore Cryptomyzus korachelti, Sappaphie mall, Myaloplerus arundinis and Myzus cemsi, as well as Cocoina, for example, Aspidiotus hederae and Lecam'um hesperidum, and also Pseudococcus maririmus; Thysanoplera, such as Heroinorhn'ps femoralis, and bugs, for example, Pieama quadrant, Dysdercus intermedius, Cimex lecrularius, Rhodm'us prolixus and Triaroma infesrans, and, furthermore, cicades, such as Euscelis bilobatus and Nephoreb rix bipuncratus.

Among the biting insects, there are chiefly to be mentioned butterfly larvae (Lepidoptera), such as Plutella maculipennis, Lymantria dispar, Euproctia chrysorrhoea and Malacosoma neustria, furthermore Mamesrra brassicae and Agrotis segerum, Pieris brassicae, Cheimatobia brumara, Torm'x viridana, Laphygma frugiperda and Prodem'a litera, and also Hyponomeuta padella, Ephesria Kuhm'ella and Galleria mellonella.

The biting insects further include beetles (Coleoprera), for example, Sitaphilus granarius, (Calandra granan'a), Leptinotarsa decemlineata, Gastrophysa viridula, Phaedon cochleariae, Meligerhes seneus, Byrurus tomentosus, Bruchidius (Acanrhoscelides obtecms), Dermesres frischi, Trogoderma granarium, Tribollum casteneum, Calandra or Sitophilus zeamais, Sregabium paniceum, Tenebria moliror and Oxyzaephilus surinamensis, and also species living in the soil, for example, wire worms (Agriotes sp.) and cockchafer larvae (Melolontha melolontha); cockroaches, such as Blarella germanica, Periplanera americana, Laucophaea or Rhyparobia maderae, Blatts orienralis, Blaberus giganreus and Blaberus fuscus, as well as Henschouredenia flexivina; furthermore Orthoptera, for example, (Fry!- lus domesu'cus; termites, such as Rericulitermes flavipes and Hymenoprera, such as ants, for example, Lasius niger.

The Diptera essentially comprise the flies, such as Drosophlla melanogasrer, Ceratitis capitata, Musca domestica, Fannia caniculan's, Phormia aegina and Cal llphom eryrhrocephala, as well as Stomoxya calcitrans; furthermore, gnats, for example, mosquitoes, such as Aedes aegypri, Culex pipiens and Anopheles stephensi.

The mites (Acan') mainly include the spider mites (Tetranychidae), such as Tetranychus relarius (Tetmnychus althaeae or Tetranychus urlicae), Pararetranychus pilosus (Panonychus ulmi), gall mites, for example, Eriphyes ribis, tarsanemides, for example,

Hemitarsonemus latus and Tarsonemus palll'dus; and, finally, ticks, such as Ornithodorus moubam.

When applied against pests affecting hygiene or stored goods, especially flies and gnats, the new compounds of the present invention are also characterized by an outstanding residual effect on wood and clay and by a good stability to alkali on limed substrates.

In the field of veterinary medicine, the new compounds according to the present invention are successfully applied against numerous noxious animal parasites (ectoand endoparasites), such as arachnids, insects and worms.

0f the ecto-parasites affecting animals, there may be mentioned of the class of Arachnidea: lxodidae, such as Boophilus microplus (strains which are normally sensitive and those which are resistant to phosphoric acid esters) and Rhipicephalus bursa; Gamasidae, such as Dermanyesus gallinae; Samoptidae, such as Sarcoptes bovis, Samoptes canis, Psoroptes ovis, Psoropres cuniculi and M yobia musculi.

As ecto-parasites of the class of insects, there may be mentioned:

Mallophaga, such as Trichodecres canl's, Damalines bowls and Eomenacanthus stramineus;

Anoplu m, such as Haematopinus eurysternus;

Diptera, such as Melophagus ovinus, and larvae of Diptera living as parasites in warm-blooded animals, such as Lucilia sericata, Lucilia cuprina, Chrysamyia chloropyga;

and larvae of warble flies, such as Hypoderma bovis.

A phaniptera, such as Ctenocephalides cam's.

As endo-parasites affecting animals, there may be mentioned of the class of nematodes;

Strongylidae, such as Oesophagostomum columbianum; Ancylostoman'dae, such as Uncinaria stenocephala and Ancylostoma caninum;

Ascarididae, such as Toxocara cam: and Toxascaris leom'na;

Trichostrongylidae, such as Haemonchus contortus and Trichlostrongylus colubriformis;

Triehuridae, such as Capillaria obsignata.

Advantageously, the active compounds according to the present invention are equally suitable as insecticides and acaricides in plant protection and also for combating hygiene pests, for example in homes, stables and store rooms.

Thus, the new compounds of the instant invention can be used as pesticides either alone or in admixture with solid or liquid carriers or diluents.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with dispersible carrier vehicles, such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granulates, etc. These are prepared in known manner, for instance by extending the active agents with dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g., surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents (cf. Agricultural Chemicals, March 1960, pages 35-38). The following may be chiefly considered for use as carrier vehicles for this purpose:

dispersible liquid diluent carriers, such as aromatic hydrocarbons (for instance, benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (for instance, chlorobenzenes), paraffins (for instance, petroleum fractions), chlorinated aliphatic hydrocarbons (for instance, methylene chloride, etc.), alcohols (for instance, methanol, ethanol, propanol, butanol, etc.), amines (for instance, ethanolamine, etc.), amides (for instance, dimethyl formamide, etc.), sulfoxides (for instance, dimethyl sulfoxide, etc.), ketones (for instance, acetone, etc.), and water, as well as dispersible finely divided solid carriers, such as ground natural minerals (for instance, kaolins, alumina, silica, chalk, i.e., calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (for instance, highly dispersed silicic acid, silicates, e.g., alkali silicates, etc. whereas the following may be chiefly considered for use as carrier vehicle assistants, e. g., surface-active agents, for this purpose: emulsifying agents, such as non-ionic and anionic emulsifying agents (for instance, polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl aryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.); and dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

As will be appreciated by the artisan, the active compounds according to the instant invention may be present in such formulations or compositions in the form of mixtures with one another and with other known active substances, if desired.

The substances according to the invention may be employed by themselves as the artisan will appreciate, in the form of their compositions with solid or liquid dispersible carrier vehicles or other known compatible active agents, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granulates which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95 percent by weight, and preferably 05-90 percent by weight of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 000001 and 20 percent, preferably 0.01 and 5 percent, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a dispersible carrier vehicle, such as (l a dispersible carrier solid, or (2) a dispersible carrier liquid preferably including a carrier vehicle assistant, e.g., surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.00001 and percent by weight of the mixture. Specifically, the active compound may be applied to a limed surface area in the foregoing field application ranges without losing the pesticidal activity of the compound even after extended periods of time in contact with such limed surface.

Furthermore, the present invention contemplates methods of combating pests, especially insects and acarids, which comprise applying to at least one of (a) such pests and (b) their habitat, a pesticidally, especially insecticidaliy and/or acaricidally, effective amount of the particular active compound of the invengenuine enrichment of the art. This unexpected superiority and the outstanding effect of the new compounds according to the present invention, when applied against a great number of pests and animal parasites,

tion alone or together with a carrier vehicle, as noted 5 can be seen from the following test results:

above. The instant formulations or compositions are applied in the usual manner, for example, by spraying, EXAMPLE AI atomizing, vaporizing, scattering, dusting, watering,

sprinkling, fumigating, and the like. It will be realized in Dmsophlla accordance with the present invention that the instant sob/en}: 3 Parts y Y l acetone compounds may be used effectively not only in plant Emulstfier: i part by weight allrylaryl polyglycol ether protection, but also in hygiene control, especially To P a smlfiblc l "'l of acme against insects and acarids and most significantly in Pf P y welght of the lf q ls connection with alkaline uu mixed with the stated amount of solvent containing the In the veterinary field, the new compounds of the stated amount of emulsifier and the concentrate is present invention are applied to known manner. f diluted with water to the desired concentration. ample, by oral administration in the form of tablets, 1 ccof the preparation of the active compound is capsules, drinks or granules; by dermal application, for applied with a pipette to a filter paper disc of 7 cm. example, by immersing (dipping), spraying, pouring on diameter. The wet disc 1s placed in a glass vessel conor powdcring; and by parenteral application, for examwill!!! Q ffllll flies (DmmPhllfl meldnogfl-flefl and pie, in the form of injections. covered with a glass p In comparison with the active compounds of After the specified period of time, the destruction is analogous constitution and of the same type of activity determined as a percentage: 100 percent means that all previously known from the literature, the new comthe flies are killed; 0 percent means that none are pounds of the present invention, surprisingly, are killed. characterized by a substantially improved effectiveness The active compounds, their concentrations, the and a considerably lower toxicity towards warmevaluation time and the degree of destruction can be blooded animals. The new compounds thus constitute a seen from the following table:

TABLE A1 [Plant damaging insects] Concen- Degree of tration destrucoi active tion after compound, 24 hours, Active compound percent percent 0 A s CH1 01 10 {L 1 Q 0.01 0 (C2Hs0): 0-N=C (Control preparation according to German Spec.

III1 s ON 0.1 100 I! I Q 0. 01 100 (CHa0)1P0N=C- 0. 001 100 0.0001 20 (According to invention) IV;..... 3 CN 0.1 100 i1 5 0. 01 100 (011110). -0N= 0. 001 90 (According to invention) v1 s 0N 0.1 100 ii I 0.01 100 (CH1O)1P-0N=CC1 0. 001 85 (According to invention) v11--." s ON 0.1 100 H l o. 01 100 (CaHs0)1P-ON= cQ-m 0. 001

(According to invention) VII;. 0 011 0.1 100 g Q 0. 01 100 011110), 0N=C- (According to invention) VIIh... 011,0 8 CN 0.1 100 0 1G 0. 01 00 P0N=O (According to invention) IX1 011.0 5 ON 0.1 100 \II 0.01 100 PON=U 0.001 100 C1- 0. 0001 CsHsO Active compound TALE A|-Continued Concentratlon f active Degree o destruc' tion after compound, 24 hours,

percent Xi--. CILO S (Accnriln to invention) ISO-(3.111 0 After the specified period of time, the degree of destruction is determined as a percentage. 100 percent means that all the caterpillars are killed, whereas 0 percent indicates none are killed.

The active compounds,their concentrations, the evaluation time and the results obtained can be seen from the following table:

TABLE A:

[Plant damaging insects] Concen- Degree of tration destruc- 01 active tion after compound. 3 days, Active compound percent percent A 4 S IO"; 0. 1 8D cnn0ni -oN:0-

(Control preparation accurdln 1 to German Spam. No. 1,052,981

1V= S UN 0.1 100 I 0.01 100 ((hlhO): -(l-N (1 0.00] 100 XVIIl 5 CN 0.1 100 {l A} 0.01 100 (0111 0): -O-N 0.001 100 IX, C11 0 S ()N 0.1 100 \11 I 0.01 100 ()-N' 13- 11001 00 0 11 0 XIX] (111:0 H UN 0.1 100 \n A: 0.01 100 ()-li.: 0.001 iso-CdLO X111;- C1130 8 CN 0.1. 100 \{L J) 0.01 100 O-N= 0.001 100 see. (341110 XV! C 11 0 0 ON 0.1 100 \L g 0.01 100 0N= 0 00 100 VI1I; C11 0 8 CN 0.1 100 \l] 4: 0.01 4 -0N= H 0 XVII; 0.1 0.01 60 Plutella Test Solvent:

EXAMPLE B 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether. 65 To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the evaluation time and the results obtained can be seen stated amount of emulsifier and the concentrate is from the following table:

TABLE 13 [Plant damaging insects] Concentra- Degree of tion desactive traction compound, after 4 days,

Active percent pereen t IV S ON 0.001 100 II P 0.0001 100 (C:Il O}1P-0N= 1H1 S UN 0.001 100 H 0.0001 110 (Cil;O)P()-N:U-

XX1 CN 0.001 100 Ii 4 0.0001 50 [C;iI O-i.so)=1()N:

XXI S ON 0.001 100 {I 1 0.0001 (CgIhO-l't): -O-N:C

VI S CN 0.001 100 {L 0. 0001 100 (C HsOh ON=C-- Cl 0.00001 20 XXII] CzlI C S N 0.001 100 XIVZ N C lhO S ON 0.001 100 \g 4 0.0001 0-N= CzHb XII: CzHiO 8 CN 0.001 100 \ll 0.0001 100 0N= lilo-OM 0 X? (EH 0 S N 0.001 X00 \{1 Q 0.0001 100 iso-C H10 vrn 0.001 I 100 diluted with water to the desired concentration.

Cabbage leaves (Brassl'ca oleraoea) are sprayed with Termite Test with the preparation of the active compound until dew Solvent: moist and are then infested with caterpillars of the diamond-back moth (Plutella maculipennis).

After the specified period of time, the degree of destruction is determined as a percentage: 100 percent vent. means that all the caterpillars are killed, whereas 0 percent means that none are killed.

The active compounds, their concentrations, the

EXAMPLE C acetone A preparation of active compound is first produced by dissolving the amount of the active compound required for the desired concentration in the above so]- 2 cc. of this solution of the active compound are applied, by means of a pipette, to a filter paper disc of about 9 cm. diameter. After leaving for 4 days to evaporate, worker termites flavipes) are placed on the filter disc.

After the specified period of time, the degree of struction is determined as a percentage: lOO percent means that all the termites are killed, whereas 0 percent means that none are killed.

The active compounds, their concentrations, the evaluation time and the results obtained can be seen from the following Table:

(Reticuliterrnes 16 pound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

5 Cabbage plants (Brassioa olemcea), which have been heavily infested with peach aphids (Myzus persicae), are sprayed with the preparation of the active compound until dripping wet.

After specified period of time, the degree of destruc- EXAMPLE D Myzus test (contact action) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether. To produce a suitable preparation of active comtion is determined as a percentage: 100 percent means that all the aphids are killed whereas 0 percent means that none are killed.

The active compounds, their concentrations, the evaluation time and the results obtained can be seen from the following table:

TABLE 1) [Plant damaging insects] Conoentra- Degree of tlon 0| destruction active after 24 compound, hours, Active compound percent percent A" (:11: 0. l

l a 2Hs0)zlU-.\'=C

(Control preparation according to Harman spec. No. 1,052,081).

1114 S (,N 0. 1 100 l U. 01 erratum-01am:

1V v S C N Dbl l 0. l 100 (cnn0P-o-x=c-/ 0. 00 00 XX]: S C N 0. 1 I00 j l 0. (ll 05 (C3H;O );P-O-N=C XX: S CN 0. l 100 U. 01 W0 (C;Hr0-iso)zl0$:-

V; S (N 00. 1 U1 rcnzonro.\'=c- -;1 0.00: 05

VI; S C N 0. 1 l 0. U1

'C;II (J P0.\'=C Cl 0. 001 70 X\'III H C 0.1 100 0. 01 100 C:lI5 ))QPUX=C 0001 20 TABLE 13-001111111100 (Plant damsging insects) Concantra- Degree of tion of destruction active after 24 compound hours, Active compound percen percent xx1n...... s "'cT '01 {l J: 0. 01 00 ((321150): -0N= 0.001

xx1v, 01 0.1 100 s on 0. 01 100 ll 1 0. 001 00 (C;H;O):PON= 0. 0001 10 x1 onto s CN 0.1 100 \g 0. 01 100 ON= 0. 001 0a 0.0001 00 iso-C;H10

XXVI C2H:0\S CN 00b: 83

l'l-CtHlzO xix, 01110 S CN 01 T00 I I 0.01 100 0-1-=c 0. 001 09 0.0001 lSD-CtH'IO A:

x11, CtHl0\fi CN 0. 1 100 0.01 100 P-o-N=c 0.001 00 lso-CaH10 XIV: CHO S CN 0. l 100 11 0.01 100 P-O--N=C 0. 001 100 XV: CgHsO 0 CN 0.1 100 \lf 1 0. 01 100 /P0N= 0. 001 cm,

v11,........ 0 ON 0.1 100 1 1 0. 01 00 (c,n,0 ,-P-o-N=c xxvn" s ox 0.1 100 N l 0. 01 100 (013.0 PON=C N0:

xxvn, s c N 0.1 100 H l 0. 01 100 1Hr0)rP0N=C xxvnn.-. s 0): 0.1 00 5; 1 0. 01 2 s PON=C EXAMPLE E the preparation of the active compound until dripping Teu-anychus gm wet. The bean plants are heavily infested with spider Solvent: 3 parts by weight acetone mites (Terranychus urticae) in all stages of develop- Emulsifier: l part by weight alkylaryl polyglycol ether. 60 After specified periods of time, the effectiveness of To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate so obtained is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgan'a), which have a height of approximately 10 30 cm., are sprayed with the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: percent means that all the spider mites are killed, whereas 0 percent means that none are killed.

The active compounds, their concentrations. the evaluation time and the results obtained can be seen from the following table:

tlon of destruction actlvu utter 48 compound hours. Active compound percent. pomant A S OH; 0. 1 50 (Known from German Spec. No. 1,052,981). III 8 ON 0. l 100 C H O O EXAMPLE F 65 number of other biting and sucking insect pests can be The outstanding activity which the compounds acan f th f ll wi g tabl cording to the invention also have against a large ioiosz om:

The outstanding effect of the products of the present process in the veterinary field against ectoand endoparasites can be seen from the following examples of spec, Rhipicephalus spec. and Amblyomma spec. are dipped in these preparations of active compound for one minute. After dipping 10 female specimens of each use. of the various species, they are transferred to petri EXAMPLE G '5 dishes, the bottom of which is covered with a filter disc Tick test of corresponding size. The effectiveness of the prepara- Solvent: 35 parts by weight ethyl glycol tion of the active compound is determined after 24 monomethyl ether hours by counting the severely afiected and dead ticks. Emulsifierz35 parts by weight nonylphenol polyglycol The degree of destruction found in this way is exether 10 pressed as a percentage: 100 percent means that all the To produce a suitable formulation, 3 parts by weight ticks are severely affected or killed at the concentraof the active compound are mixed with 7 parts of the tion used, whereas 0 percent means that none of the stated solvent/emulsifier mixture and the emulsion conticks shows indications of any effect. centrate so obtained is diluted with water to the desired The active compounds, concentrations and parasites concentration. 15 tested and the results obtained can be seen from the Engorged adult female ticks of the species Boophilus following table:

TABLE 0 eflal t iz a 01333- Active compound Parasite @3 31 5 CN Bodphilus micropius, normally resistant strain 2. 5-5 (C|HlO)sfl'0N=- IV; Boflphilus mtcroplua, strain resistant to a number of phosphoric acid esters- 5 S C N Bodphilus deealoratlu 5 canoni o-rhc fffiifiit 35%;: i2 Rhipicuphalus stmusn 25 Amblvmmna hctraeum 260 XIX. e. i-C;H 0 S ON Bodphilus micmplus, normally sensitive strain 1 i 0N=J7 omo I XIV; 01H; 8 ON Same as above 1 CIHIO/ x. 1 0.1110 5 CN ..do 1

3 CHsO v1, s ON Mao 1o 0,H.0).i0N=o--ci xxx. s CN .do 1o (n-CIH1O):i O-N=JJ xxxl i-0,H10 s CN do 2s i-onrmn x11. e. 0,1150 s cm do 1 i-C|H10 xx, s CH -do 10 (i-O;HOJ,i"-ON= x1, i-C;H O s ON do 2.5

i -O- flB-Q-QI CHIO/ v, s ON -...do s00 (OHa0)|i 0N=( 7Ci xvnrt--." CN d0 10 TABLE -Continued oflest rzi critical 001100- Active compound Parasite Emit III. CHlo s on ..AO: w

i ..=t@ CHsO xxIv, 01 d0 5 s CN (CzH|0):=i 0N=('3 EXAMPLE 1 Emulaifier: 35 parts by weight nonylphenol polyglycol Poultry mite test ether Solvent: 35 parts by weight ethyl gly To produce a suitable formulation, 3 parts by weight monomethyl eth of the active compound are mixed with 7 parts of the Emulsifier: 35 parts by weight nonylphenol polyglycol ether To produce a suitable formulation, 3 parts by weight of the active compound are mixed with 7 parts by weight of the stated solvent and the emulsion concentrate so obtained is diluted with water to the desired concentration.

Larvae, nymphs and adults of Dermanyrsusgallinae, which have been placed on filter paper strips, are inten' sively sprayed with these preparations of active compound. The mites are transferred, with the filter paper, to cylinders of "Plexiglas, one edge of which is covered with a very fine Perlon gauze, whereas the other is placed on a glass disc to prevent the mites from escaping. (Plexiglas" and Perlon are Registered stated solvent/emulsifier mixture and the emulsion concentrate so obtained is diluted with water to the desired concentration.

Dogs which are infested with Sal-copies cam: in all stages of development, are dipped into the preparation of active compound, or cattle which are infested with Sampler bow: in all stages of development, are sprayed with this preparation. After 72 hours, the effectiveness of the preparation is determined by examining the host animals for mites which are still alive, the degree of destruction of the parasites being expressed as a percentage.

The active compound, its concentration, the parasites and the results obtained can be seen from the following table:

Trade Marks.)

After the specified period of time, the effectiveness of the preparation of active compound is determined TABLE H2 100% effective concentra- Active compound Parasite tion, p.p.m.

IV" S OH Sci-copies umfr a 500 Sarcoptcs bovisnfl fl soh -0N= I EXAMPLE H.

Sucking mite test/Psoroptes cuniculi Solvent: xylene by counting the dead mites. The degree of destruction found in this way is expressed as a percentage: 100 percent means that all the mites are killed, whereas 0 percent means that none are killed.

The concentration of active compound, the evaluation time and the degree of destruction can be seen from the following table:

To produce a suitable preparation of active com- 50 pound, a definite amount by weight of active compound is mixed with a definite volume of the solvent and 1 part by volume of this solution is diluted with i0 parts by volume of liquid paraffin to the desired concenn'ation.

TABLE H1 Concentra- Degree of tion of destruction active after 24 compound, h u Active compound ppm. percent v H E IN i% canton: 0N= 100 100 so m 10 as EXAMPLE H, Drops of the preparation of active compound so ob- Sarcoptidae test tained are put on slides and about 30 mites of the spe- Solvent: 35 parts by weight ethyl glycol cies Prompts: curricula in all stages of development are monomethyl ether placed thereon 24 hours later. After a further 72 hours,

27 28 the concentration is determined at which all the mites pound, 30 parts by weight of the active compound conare severely affected or killed (efl'ect: good). cemed are mixed with the stated amount of solvent The active compounds, the tested concentrations containing the stated amount of emulsifier and the conand the effective critical concentrations can be seen centrate so obtained is diluted with water to the desired from the following table: 5 concentration.

TABLE Ha Concentratlon. Active compound ppm Eflect IV S CN 100 Good. H 1: 50 D0. (C :H O):POZ\'= 25 Partial efiect.

VII CN 100 Good. U j: 50 D0. unmonP-o-x: 25 Do. 12. Do.

XIvs s. Cal-I 5 CK lofl D0. E? r 50 Do. P0-N:C D0.

X1 iso-(hFhO 5 C N 100 Do.

T /PON= C1130 v1, .s 5 K 100 D0.

Li (C2H O):PON=CCl XII: is0-C;H1O\S TN 100 D0.

/igwo x:- CgHsO XIX iso-C;ll.-O CN 100 Do.

PO.\' -C C1110 l XVIII,- c l S X 100 D0, Do

XXXI; S C N 100 D0.

IX; CIIKQ (TN 100 Do 0 5|) D04 P- -x: l GzHaO XIII; l. secl-4H{.Q S C.\' lOO 1J0,

,PON=C- cum XXXIII l. II-C4H0O\ 5 (IN 100 D0 EXAMPLE H Mice are dipped into this preparation of active compound twice for 5 seconds with an interval of 5 Range est/mouse seconds. The animals are heavily infested with Myobia solvent: 35 Parts y Weight ethyl glycol monomethyl musculi in all stages of development. After 48 hours,

ether the concentration is determined at which all the mites Bmulsifier: 35 parts by weight nonylphenol polyglycol ar kill d,

edit; The active compounds and the effective concentra- To produce a suitable preparation of active comtions can be seen from the following table:

a IABLE H4 Concentration at which all the mites were killed, Active compound ppm.

I H F CN 200 c,H,0)z1 -o-N=cvm 1 CN 400 (cm,0 .P-o-N- -o XIV1 CzHs CN 2% PON= CzHsO XI .iSO-C :H\ C1? 200 W l t a t XXXIII S CN 200 czH.0),i -o-N=c-@-c1 X111 iS0-C:H1O S (EN 200 CzHsO XX 5 CN 400 i (iso-C;Hr0);PO-,\'=C

XXIV. l 200 S CN l (cznlonrox= IX. C1130 5 (EN 400 CzHaO XXXII: n-CaHvO 9 93 200 CzHsO xxlxt s, CS 400 (C2H50):POX=C OCH3 cattle Trichodecter scalan': EXAMPLE I llteep Danwlinea ovir Biting lice test do Trichodlcrer mm: Solvent: parts by weight ethyl glycol monomethyl 5 5 fowl flown-MM! S'Mmivww ether are sprayed with or bathed in the preparation of active compound. After 24 hours, the'efi'ectiveness of the preparation of active compound is determined by ex amining the host animals for parasites which are still alive, the degree of destruction of the parasites being given as a percentage.

The parasites, the concentrations of active compound and the results obtained are summarized in the following table:

TABLE 1 $333233; sn gu flmil ut Active compound Parasite cmp., ppm. 24 hours, par;

68!! ON Trichodecteucaluria i% {L A 25 mo (c H 0),= ON= Dumulmw Mia Trichodwm cunt: 50 100 to 100 100 100 Eomenacemhm atmmirmu" 50 100 00 EXAMPLE K, centrate so obtained is diluted with ovine or bovine t serum to the desired concentration. m parasmzmg fly larvae About fly larvae (Chrysomyia chloropyga or La- P by welsh PolYgIycol cilia .rericala or Lucilia cupnna) are placed in a small monoethyl ether Emuleifier: 35 parts by weight nonylphenol polyglycol ether To produce a suitable preparation of active com- 20 test tube containing 2 ml. of the preparation of active compound adsorbed in cotton wool. After 48 hours, the degree of destruction is determined as a percentage: 100 percent means that all the larvae are killed, whereas 0 percent means that none are killed.

The active compounds. their concentration: and the results obtained can be seen from the following table:

TABLE Kl Concentraon of Degree of destruction, percent active compound, Ckrwomyia Lucilia Lucille Active compound p.p.m. chloropyga aerimla cu prim: '1 4 5 CN 1.0 100 1m 1m 11 I 0. 5 100 100 (C;H;O)1POI\=C 0.26 0 50 50 11!, S CN 1. 0 100 ry l 0. 5 a a (CH;O),P0N=C 0.25 50 XIV; i CzHs 3 C .0 r r V t o t \I I 0. 5 50 r t t V l r y /P-0N=C 0.25 50 a. a r rHaO v D X9 e. iSO-CuHrO 5 CN 1. U H I o. 5 /PON=C 0. 25 CHaO V1 S ON 1.0 IE I o. e (C,H;0J:P-O-N=C Cl 0. 25

XII iso-CzHzO S CN 1.0 l! I 0. 5 /P-ON=C 0. CIHIO XX; S CN 1. 0 ll 0. a lSO-(CzH OhP-O-N: 0. 25

V4 S CN 1. 0 50 4 t 4 H l 0. 5 50 (CHaO): PON=C 01 XI; i50-CiH1O 8 CN 1. 0 1!!) 1! o. a 1m /PON= Cl 0.26 100 CHuO XIX. ls0-C;H1O S ON 1.0 100 ii 1 0.15 100 P-0N=C 0.25 50 CHaQ i XVIII| S CN 1. 0 100 v Ii 0. 5 100 4 l a a l .i (C:H50):PON=C 0.25 60 t t XXIX3 s CN 1. o 100 100 H l o. 5 50 50 (C:H50):PON=C ClCH; 0.25 0 (50 u lows:

2L 7 Example K,

Systemic test for parasitizing fly larvae in mice EXAMPLE K,

Systemic test with warble fly larvae of cattle Solvent: 35 parts by weight ethyl glycol monomethyl Solvent: n-butanol ether To produce a suitable preparation of active com- Emulsifier: 35 pans by weight nonylphenol polyglycol pound, i0 parts by weight of the active compound are ether mixed with 90 parts by weight n-butanol.

To produce a suitable preparation of active com- You ng cattle which are heavily infested with larvae q zg ag 2 i gg i a of Hypoderma bovis, are treated with the preparation of :3 32 35 'z active compound by pouring the preparation on to the mined 9'33" :Tfi' s 5 5 i; t 3 median iine of the animal, approximately between the m f u five to i leied T test withers and the root of tail. Three weeks after the treatanigluals zfi fi z a cc of thisagfiulsion ment, the number of larvae which are still alive is deter- 0.5 ml. of the preparation of active compound are the effewvcmss mus calculamd as a administered by means of a pharyngoprobe or by ing tramuseular or subcutaneous injection to male mice The active mp d. lhfl dost? pp the P having a weight of g. At various time intervals alter and the percentage effect can be seen from the followthe treatment, the mice are killed and muscular test 8 b e:

TABLE K3 Degree oi destruction Dose, alter2l days, Active compound Parasite mgJkg. percent 8 (IN Hvpodrrma anvil 86 Iv (c1m0 ,i -0N=c- Hupoderma bovis 10 50 sam les are taken, which are filled into small test tubes. EXAMPLE K,

in which 20 freshly hatched fly larvae of the species Lucilia sen'cata are then placed. After 48 hours, the degree of destruction is determined as a percentage.

The active compounds tested, the dose applied and the 100 percent efl'ective critical concentration can be seen from the following table:

TABLE K:

2%.:tsfirrfii's sz s22fie Active compound mgjkg. Orally Intramusc. Subcutan.

IV S C.\ 25.0 (c,H,0),i 0-x= 0 IX; CzHsO C.\ 25.0

CHzO

XIII iSO-CsHrO CN 250 CHaO VI; CN 251) (c,mo ir -o-x= r-ci XIX: I .e iSO-CsHrO CN 25.0

C1110 (In XVIII. s (3N 25.0

(CzHgO):PO.\'=C- XXXHH..." CH1 3 (IN 12.5

CzHgO To produce a suitable formulation, 3 parts by weight of the active compound are mixed with 7 parts of the stated solvent! emulsifier mixture and the emulsion concentrate so obtained is diluted with water to the desired concentration.

Sheep which are heavily infested with Melophagus ovinus, cattle which are heavily infested with Haematopinus eurystemus and dogs which are heavily infested with Ctenocephalides canis, are sprayed with these preparations of active compound. After 24 hours, the effectiveness of the preparations is determined by examining the host animals for parasites which are still alive, the degree of destruction of the parasites being expressed as a percentage.

The parasites, the concentrations of the active compound and the results obtained can be seen from the following table:

EXAMPLE L,

Ancylostomatidae test/Uncinaria stenocephala The amount of active compound to be applied is administered as pure substance in capsules to the animals (dogs) to be treated. These are heavily infested with worms of the species Uncrnan'a stenocephala. When the prepatent period has elapsed, the effect of the preparation of active compound is determined by counting the worms expelled after treatment and those remaining in the animal and calculating therefrom the percentage of expelled worms.

The active compound and parasites tested, the dosage applied and the percentage effect can be seen from the following table:

TABLE L7 l iii um )er mg, z. crcenta I Active compound Parasite of animals animals p cfit \II; V c a t (125. Unrinuriaatenoccphula t t 1 0 1 l0 '7 C:N-OP(OC2H5): 4 i4 3 100 l 50 l00 TABLE Kl Concentration oi Degree of active destruction compound, after 24 hours, Active compound Parasite p.p.m. percent 5] (IN Melophugua uvinuaun c M! 100 100 1 T a 100 100 IVnn-u e Harmatopz nus cury sternua.. 50 100 108 100 i 5 100 Cta nocepha lzdea cums. A 4 m 100 5 50 EXAMPLE l. EXAMPLE L,

Ascarid testfloxocara canis The amount of active compound to be applied is administered as pure substance in capsules to the animals (dogs) to be treated. These are heavily infested with worms of the species Toxocam canis. When the prepatent period has elapsed, the effect of the preparation of active compound is determined by counting the worms expelled after treatment and those remaining in the animal and calculating therefrom the percentage of expelled wonns.

The active compound and parasites tested, the dosage applied and the percentage effect can be seen from the following table:

TABLE Li Dos, N uinhvr m mkxa o p rc -ntagc Active compound Parasit 0! animals animals efi ct \IIq. t. C.\ 0 Anculoaloma caninum,. 1 5 1;] l 10 C:n\'0P- CzH:/z 5 15 74 ii 25 Note-The symbol 4: means thP average percmtag eficct obtained from several t -st r ults,

TABLE L;

Dose, N umber mg./kg. a percentage Active compound Parasite animals animal eflect VII; ON 0 Torocamcanir 2 5 98 J: {l 2 94 NO- (OC:H5): 6 8B 3 100 2 100 0.16 per cent by weight alginic acid EXAMPLE -4 lo Formulation auxiliaries: p py s y ester Asearid testl'loxascaris leonina The amount of active compound to be applied is administered as pure substance in capsules to the animals (dogs) to be treated. These are heavily infested with worms di AND the species Toxarcarr's leomna. When the prepatent period has elapsed, the effect of the preparation of active compound is determined by counting the worms expelled after treatment and those remaining in the animal and calculating therefrom the percentage of expelled worms.

The active compound and parasites tested, the dosage applied and the percentage effect can be seen from the following table:

0. [6 per cent by weight dioctyl sodium sulphosuccinate Water ad I00 per cent by weight The active compound to be applied is introduced into ml. of the above mixture and suspended therein by means of an ultrastirrer.

Lambs which are heavily infested with worms of the species Haemonchus conrortus, Trichosrrongylus calubnformis and Oesophagostomun columbianum are treated orally with the preparation of active compound so obtained. When the prepatent period has elapsed, the effect of the preparation is determined by counting the worms expelled after the treatment and those remaining in the animal and calculating therefrom the EXAMPLE M Gestric-intestinal worm test/sheep The following mixture is prepared:

percentage of expelled worms.

The active compounds, parasites, dosage employed and the effect obtained can be seen from the following table:

n-CaHzO TABLE M Dose, Percentage Active compound Parasite rngn/kg. elTt-ct IV HU F (IN 10 50 Hnemonchua conlortus. 25 z s "0- C 50 J 10 50 Trzchoatmngulua coluhrijormia.. i. 25 85 50 100 Oeaopharostomum columbianum s i 50 70 HI i i t i S Haemonchua crmtortua. i H i. 250 loo (CIi;O}==P-UN=C X CH30 C.\' Haemonchus cantor/us i i i. 20 100 PN=CO iCZHTC \I w. 7a.. CN Haemonchu; conform-r. .r 20 100 rc2IL-o=1-o-.\'=c-( 01 XX, V .7 H. F (N Haemonchus contortua. 200 100 'i-CaH1 'J)1:PU-N=C-% =2 X14 i is CHaO CN Haemonchua contorturu 50 100 /P we r? c1 i-ciHm XXX C'HiQ CN Hflemunchua contortua. 50 100 pair 

2. Method of combating insects or acarids which comprises applying to at least one of (a) such pests and (b) their habitat, an insecticidally or acaricidally effective amount of a phosphorus-containing Alpha -oximino-aryl acetic acid nitrile having the formula: in which R1 is selected from the group consisting of alkyl having one to six carbon atoms, and haloalkyl having one to six carbon atoms, R2 is selected from the group consisting of alkyl having one to four carbon atoms, alkoxy having one to four carbon atoms, haloalkoxy having one to four atoms, lower alkyl amino, di(lower) alkyl amino, phenyl, phenoxy, cyclohexyl, and cyclohexyloxy, R3 is selected from the group consisting of phenyl, naphthyl, and substituted phenyl which is substituted with substitutents selected from the group consisting of mono-, di-, and tri-halo, lower alkyl, lower alkoxy, lower alkyl mercapto, nitro, and mixtures thereof, and X is selected from the group consisting of oxygen and sulfur.
 3. Method according to claim 2 wherein said nitrile in used in the form of a mixture with a dispersible carrier vehicle selected from the group consisting of (1) a dispersible finely divided solid and (2) a dispersible liquid containing a surface-active agent, said nitrile being present in an amount substantially between about 0.00001 and 20 percent by weight of the mixture.
 4. Method according to claim 2 wherein such compound is 0,0-dimethyl-thionophosphoryl- Alpha -oximino-phenylacetic acid nitrile.
 5. Method according to claim 2 wherein such compound is 0,0-diethyl-thionophosphoryl- Alpha -oximino-phenylacetic acid nitrile.
 6. Method according to claim 2 wherein such compound is 0,0-dimethyl-thionophosphoryl- Alpha oximino-4-chlorophenylacetic acid nitrile.
 7. Method according to claim 2 wherein such compound is 0,0-diethyl-thionophosphoryl- Alpha -oximino-2-chlorophenylacetic acid nitrile.
 8. Method according to claim 2 wherein such compound is 0,0-diethyl-phosphoryl- Alpha -oximino-phenylacetic acid nitrile.
 9. Method according to claim 2 wherein such compound is 0-cyclohexyl-0-methyl-thionophosphoryl- Alpha -oximino-phenylacetic acid nitrile.
 10. Method according to claim 2 wherein such compound is ethyl-0-ethyl-thionophosphonyl- Alpha -oximino-phenylacetic acid nitrile.
 11. Method according to claim 2 wherein such compound is 0,0-diethyl-thionophosphoryl- Alpha -oximino-4-methylmecapto-phenylacetic acid nitrile.
 12. Method according to claim 2 wherein such compound is phenyl-0-ethyl-thionophosphonyl- Alpha -oximino-phenylacetic acid nitrile.
 13. Method according to claim 2 wherein such compound is 0,0-diethyl-thionophosphoryl- Alpha -oximino-4-nitrophenylace acid nitrile.
 14. Method according to claim 2 wherein such compound is 0,0-diethyl-thionophosphoryl- Alpha -oximino-1-naphthylacetic acid nitrile.
 15. Method according to claim 2 wherein such compound is 0,0-diethyl-thionophosphoryl- Alpha -oximino-4-methoxyphenylacetic acid nitrile.
 16. Method according to claim 2 wherein such compound is N-isopropyl-0-isopropyl-thionophosphorylamido- Alpha -oximinophenylacetic acid nitrile.
 17. Method according to claim 2 wherein such compound is 0,0-di(2-chloroethyl)-thionophosphoryl- Alpha -oximino-phenylacetic acid nitrile.
 18. Method according to claim 2 wherein such compound is 0-phenyl-0-methyl-thionophosphoryl- Alpha -oximino-phenylacetic acid nitrile. 